JPS61223015A - Resin complex particles, their production and composition for coating - Google Patents

Abstract

PURPOSE:A polyaddition type ethylenic compound is polymerized in the presence of a three-dimensional polymer of a specific particle size to give composite resin particles where the polymer polymer particles are impregnated with a part of the compound and the other has a form expanding outward. CONSTITUTION:The solution polymerization of (A) a polyaddition type ethylenic monomer is carried out in the presence of (B) 3-dimensional polymer particles of 0.01-10mu particle sizes to give the objective particles where the particles are impregnated with a part of the monomer and the other forms a plurality of straight-chain polyesters extending outward from the particle bodies. The particle of component A is preferably made of a polycondensation resin such as polyester or amino resin and polymerization resin such as acrylic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to composite resin particles and a particle dispersion composition comprising the same and an organic solvent.

(Prior Art) Resins conventionally used in coating compositions can be roughly divided into three types: soluble resins (including water-soluble resins), colloidal dispersion resins, and particulate resins.

Dissolvable resins are extremely effective as resins for paints because they have the ability to form binders, pigment dispersants, and flat continuous films, and have been widely used as resins for oil-based paints.

However, in recent years, as social needs such as resource conservation, energy conservation, and environmental conservation have increased, the use of oil-based paints has been restricted, and as a result, commercial quality water-based paints, high solid paints, powder paints, and There is a growing movement towards body paints.

When soluble resins are used for such new paints, they are insufficient in terms of painting work and film performance.

Attempts have been made to develop colloidal dispersion resins mainly for use in water-based paint systems, but they are insufficient in terms of workability, stability, etc., and are not currently mainstream resins for paints. .

Particulate resins mainly include emulsions, microgels, NAD, and powder resins, and are used as water-based paints that meet social needs for resource saving, energy saving, and environmental protection.
It is attracting attention as a promising technology for high solid paints and powder paints. These are used alone or mixed with soluble resins, and are used as binders, rheology modifiers,
Alternatively, it acts as an extender (polymer filler) and forms a coating film that exhibits high performance physical properties.

(Problems to be Solved by the Invention) However, when particulate resin is used alone, it has the disadvantage that it does not form a uniform film or only forms an insufficient film, making it impossible to obtain a good coating film appearance. has. In addition, when using a mixture of a soluble resin and a soluble resin, the interfacial interaction between the particles and the soluble resin is large, so the viscosity of the entire system may increase significantly compared to when the soluble resin is used alone. Care must be taken when using it.

An object of the present invention is to provide a new composite resin that significantly improves the drawbacks of the various coating resins mentioned above.

That is, the object of the present invention is to exhibit good coating workability and storage stability when used alone or in combination with other general-purpose resins, not only in the above-mentioned conventional paint systems but also in new paint systems. The object of the present invention is to provide novel composite resin particles that form a uniform film with good appearance, and a particle dispersion composition comprising composite resin particles and an organic solvent.

(Means for solving the problem) The present inventors have proposed a combination of a three-dimensional particle main body and a linear polymer, in which a part of the linear polymer penetrates into the inside of the three-dimensional particle. We discovered that the new composite resin particles have a relatively low solution viscosity, form a uniform coating even when used alone, and have excellent compatibility with other resins, making them extremely useful resin particles in the paint field. The present invention has now been completed.

That is, according to the present invention, a three-dimensional polymer particle main body having a diameter of 0.01 μm to 10 μm and a large number of straight chain-like particles, some of which penetrate into the particle main body and some of which extend outward from the particle main body. Composite resin particles comprising a polymer group, a method for producing the same, and a resin composition for paint are provided.

The novel composite resin particles of the present invention have a particle size larger than that of the original three-dimensional polymer particles by combining a particle main body made of a three-dimensional polymer with a linear chain, and are resistant to change in particle size. The maximum range is 2.5 times.

Furthermore, the solution viscosity is significantly lower than that of a composition in which a three-dimensional polymer and a linear polymer are simply blended without being combined.

The particle main body made of the three-dimensional polymer used in the present invention is made of condensed resin such as polyester resin, epoxy resin, or amino resin, and polymerized resin such as acrylic resin or vinyl resin and has a diameter of 0.01 μm to 10 μm.
It is characterized by being a polymer particle with a three-dimensional structure. Such crosslinked resin particles can be advantageously produced by various methods well known to those skilled in the art, such as emulsion polymerization, NAD polymerization or solution polymerization. Depending on the manufacturing method, it may be used as is, isolated, or crushed.

Further, the linear polymer is characterized in that it is a linear polymer obtained by addition polymerization of an addition polymerizable ethylene compound.

Examples of addition-polymerizable ethylene compounds include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and their esters, as well as styrene, vinyltoluene,
Acrylonitrile, vinyl acetate, acrylamide, N-
It may also contain related monomers such as methylol acrylamide. In addition, especially when using acrylic esters or methacrylic esters, the following general formula % formula % (However, in the above formula, 8 R is H or CH3, R is 1 carbon number
~15 saturated hydrocarbon groups) (e.g., methyl acrylate, methyl rutacrylate, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, etc.); Those having a hydroxyl group in R2 of the general formula, such as acrylic acid 2
-Hydroxypropyl, 2-hydroxypropyl methacrylate, acrylic M2-hydroxyethyl, methacrylic Ig! Examples include 12-hydroxyethyl.

As described above, the composite resin particles of the present invention have a structural feature in which the linear polymer partially penetrates into the three-dimensional polymer particle body and partially extends outward.

Such composite resin particles can be easily produced by solution polymerization of an addition polymerizable ethylene compound in the presence of three-dimensional polymer particles. In other words, a radical polymerization initiator such as an organic peroxide or an organic azo compound, a solvent, three-dimensional polymer particles, and a polymerizable monomer are charged all at once into a reactor and polymerized by heating, or an organic solvent is charged into a reactor and heated. In this case, solution polymerization methods well known to those skilled in the art are conveniently used, such as a method of dropping an initiator, three-dimensional polymer particles and monomers, or a combination thereof.

The composite resin particles of the present invention obtained by such a method are not simply three-dimensional polymer particles with a linear polymer attached to them, but as described above, a part of the linear polymer is inside the three-dimensional polymer particles. It has a special structure that has been invaded, and this fact has been proven, for example, by observation under a microscope.

The ratio of the three-dimensional polymer and the linear polymer constituting the novel composite resin particles of the present invention can be varied widely depending on the application, type of polymer, etc., but usually 100 parts by weight of the former and 5 to 1000 parts by weight of the latter. selected within the range.

However, it is also possible to roughly increase or decrease the latter ratio if desired.

The composite resin particles of the present invention are used for paints in the form of being dispersed in an organic solvent. In this case, the solvent may be any organic solvent commonly used in paints, but usually toluene, xylene, etc. Aliphatic hydrocarbons such as aromatic hydrocarbons, alcohols, ethers, esters, ketones, etc. are suitable.

The composite resin particles and the particle dispersion composition composed of them and an organic solvent in the present invention can be used alone or dispersed in other resin vehicles not only in conventional paint systems but also in new paint systems. It is.

(Operation/Effect) The present invention has a novel structure in which particles made of a three-dimensional polymer and a linear polymer are composited by a solution polymerization method, and the linear polymer partially penetrates into the interior of the particle from the particle surface. By this, we have succeeded in significantly improving the various problems of conventional paint resins mentioned above, and achieving excellent effects on viscosity, coating film appearance, workability, stability, film forming properties, etc.

(Example) The present invention will be explained in further detail with reference to production examples and examples below.

In Hagane, all parts mean 111 parts.

Production example 1 (!J3ti of particles (1) made of three-dimensional polymer)
200 parts of deionized water, 3 parts of sodium lauryl 4111m, and 1 part of ammonium persulfate were placed in a glass reactor equipped with a thermometer, reflux condenser, nitrogen gas inlet tube, and stirrer, and heated to 80 to 85°C while bubbling nitrogen gas. 40 parts of methacrylate and 20 parts of styrene were heated to
A monomer mixture consisting of 20 parts of isopropyl acrylate and 20 parts of ethylene glycol methacrylate was added dropwise over 1 hour, and stirring was continued for 1 hour. Water was distilled off under reduced pressure from the emulsion composition thus obtained, and the average particle size was 110 mμ, and the crosslinking density was 1. olX 10'
Particles (1) consisting of mol/g three-dimensional polymer
Got 100 copies.

The particle size was determined by quasi-elastic light scattering measurement using laser light.

Shelf 4! The density was calculated using the following formula.

Production Example 2 (Production of particles (2) made of three-dimensional polymer) Production of dispersion stabilizing resin 191 parts of ethyl taurine, 140 parts of ethylene glycol, 170 parts of triethylene glycol, 331 parts of adipic acid, 168 parts of phthalic anhydride and 40 parts of xylene are charged and the temperature is raised. Water produced by the reaction is azeotroped with xylene and removed. The temperature was raised to 190° C. over about 2 hours from the start of reflux, and stirring and dehydration were continued until the acid value equivalent to carboxylic acid became 10 or less to complete the reaction. The obtained polyester resin for dispersion stabilization had an acid value of 79, a hydroxyl value of 79, and an Mn of 708.

(Production of particles (2)) In a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas introduction tube, and a stirrer, 150 parts of dehydrated ionic water, 15 parts of the above polyester resin for dispersion stabilization, and 2 parts of dimethylethanolamine were added. 1 part was charged and dissolved while stirring and maintaining the temperature at 80°C. Then n-butyl acrylate 20
A mixture of monomers consisting of 40 parts of styrene, 40 parts of ethylene glycol methacrylate, and 1 part of azobiscyanovaleric acid dissolved in 20 parts of deionized water and 0.7 parts of dimethylethanolamine was added dropwise over 1 hour. Stirring was then continued for 1 hour. Water was distilled off under reduced pressure from the emulsion composition thus obtained, and the average particle size was 40.
110 parts of particles (2) made of a three-dimensional polymer having a mμ crosslink density of 2.02×10′ mol/g were obtained.

Production Example 3 (Production of Particles (3) Made of Three-Dimensional Polymer) In the same glass reactor as used in Production Example (1), 170 parts of dehydrated ionic water and 5 of the polyester resin for dispersion stabilization in Production Example 2 were added. and 2 parts of dimethylethanolamine were charged and dissolved under stirring while maintaining the temperature at 80°C to 85°C.Then, a mixture consisting of 30 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 40 parts of styrene, and 10 parts of ethylene glycol methacrylate was added. A mixture of monomers and 1 part of azobiscyanograss flJ dissolved in 0.7 parts of deionized water and dimethylethanolamine was added dropwise over 1 hour, and stirring was continued for 1 hour. Particles (3) made of a three-dimensional polymer having an average particle diameter of 150 mμ and a crosslinking density of 5.05×10′ mol/σ by azeotropically distilling the water in the emulsion composition with xylene and distilling it off under reduced pressure, replacing the dissolved IJi with xylene. 330 parts of a xylene dispersion (solid content 30%) was obtained.

Production Example 4 (Production of particles (4) made of three-dimensional polymer) 98 parts of maleic anhydride and 106 parts of diethylene glycol were charged into the same glass reaction vessel as used in Production Example 1, and the mixture was heated while blowing nitrogen gas. The mixture was heated and stirred at 190°C to 200°C for 6 hours to obtain diethylene glycol malate having an acid value of 30. On the other hand, add 1 part of benzoyl peroxide to 50 parts of 1,4-butanediol divinyl ether, dissolve it, mix the previously obtained diethylene glycol malate uniformly, and heat it at 70°C for 1 hour. A gelled product (unsaturated polyester resin) is obtained. After the reaction, the gelled product was coarsely crushed, then finely crushed in a ball mill, and sieved to give an average particle size of 6 μm, a crosslinking density of 1, and 39×10−3 1
150 parts of particles made of a three-dimensional polymer of 01/(J were obtained.

Example 1 In a glass reaction vessel similar to that used in Production Example 1, 300 parts of the xylene dispersion of particles (3) made of the three-dimensional polymer obtained in Production Example 3, a styrene part, and 5 parts of n-butyl acrylate were placed. 1 part, 2-parts of methacrylic acid, 2 parts of droxyethyl, and 0.15 parts of azobisin butyronitrile were heated at 110℃ for 5 minutes.
A composite resin particle dispersion was obtained by heating for a time W1.

The particle size of this dispersion was 152μ, which was larger than the particle size of the original three-dimensional polymer particles (3). Xylene was removed from this dispersion by spray drying to form composite resin particles. Obtained.

Example 2 In a reaction vessel similar to Example 1, 10 parts of particles (1) made of the three-dimensional polymer obtained in Production Example 1, 27 parts of styrene, 4 parts of n-butyl acrylate, and 27 parts of 2-functional tylhexyl acrylate were added. 13.5 parts and 2-methacrylate and droxyethyl
1 part, 4.5 parts of acrylic acid, and 100 parts of xylene.

Next, 6 parts of azobisisobutyronitrile was charged, and 12 parts of azobisisobutyronitrile was added.
The mixture was heated and stirred at 5° C. for 3 hours to obtain a xylene dispersion composition of composite resin particles having a resin acid value of 35 and a solid content of 50%.

An acrylic resin varnish was produced by the same operation and method except that particles (1) made of three-dimensional polymer were not used, and particles (1) made of three-dimensional polymer 10
A comparative composition was obtained by stirring and mixing with a laboratory stirrer.

A comparison of the properties of the two is shown.

The results show that the composite resin particles have a larger particle diameter than particles made of a three-dimensional polymer, and have a lower viscosity than a mixture of particles made of a three-dimensional polymer and the acrylic resin varnish.

The viscosity was measured at 20°C using an E-type viscometer.

Example 3 50 parts of three-dimensional polymer particles (2), 10 parts of styrene, 10 parts of methyl methacrylate, 21 parts of n-butyl acrylate, 8 parts of acrylic M-2-hydroxyethyl, and 1 part of acrylic acid. A xylene dispersion composition of composite resin particles and a composition for comparison were obtained in the same manner as in Example 2 except that 100 parts of xylene and 5 parts of azobisbutyronitrile were used.

Although the former had a particle size 1.2 times larger than the latter, it was found that the viscosity was lower.

Example 4 80 parts of three-dimensional polymer particles (4), 6 parts of styrene, 4 parts of n-butyl acrylate, 6 parts of 2-ethylhexyl acrylate, and methacrylic! A xylene dispersion composition of composite resin particles and a composition for comparison were prepared in the same manner as in Example 2 except that 3 parts of 12-hydroxyethyl, 1 part of acrylic acid, 100 parts of xylene, and 1 part of azohisisocyanobutyl were used. I got it. Although the former had a larger particle size than the latter, it was found that the viscosity was lower.

Based on electron optical microscope observation.

patent application agent

Claims (6)

[Claims] (1) A three-dimensional polymer particle main body with a diameter of 0.01μ to 10μ, and a large number of linear polymer groups that partially penetrate into the particle main body and partially extend outward from the particle main body. Composite resin particles consisting of (2) The composite resin particle according to claim 1, wherein the three-dimensional polymer particle main body is made of a condensation resin such as a polyester resin, an amino resin, and a polymer resin such as an acrylic resin. (3) The composite resin particles according to claim 1, which are composed of a polymer of a linear polymer addition-polymerizable ethylene compound. (4) An addition-polymerizable ethylene compound is solution-polymerized in the presence of three-dimensional polymer particles having a diameter of 0.01 μm to 10 μm; A method for producing composite resin particles comprising a large number of linear polymer groups in which part of the polymer group penetrates into the particle main body and part of which extends outward from the particle main body. (5) A three-dimensional polymer particle main body with a diameter of 0.01μ to 10μ and a large number of linear polymer groups, some of which penetrate into the particle main body and some of which extend outward from the particle main body. A paint resin composition made by dispersing composite resin particles in an organic solvent. (6) The composition according to claim 5, wherein the organic solvent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones and esters.